EP0255201A2 - Formieren von Elektroden - Google Patents

Formieren von Elektroden Download PDF

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Publication number
EP0255201A2
EP0255201A2 EP87303942A EP87303942A EP0255201A2 EP 0255201 A2 EP0255201 A2 EP 0255201A2 EP 87303942 A EP87303942 A EP 87303942A EP 87303942 A EP87303942 A EP 87303942A EP 0255201 A2 EP0255201 A2 EP 0255201A2
Authority
EP
European Patent Office
Prior art keywords
precursor
electrodes
electrode
oxidized
terminal electrodes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87303942A
Other languages
English (en)
French (fr)
Other versions
EP0255201A3 (de
Inventor
Harvey N. Seiger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CBS Corp
Original Assignee
Gould Inc
Westinghouse Electric Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gould Inc, Westinghouse Electric Corp filed Critical Gould Inc
Publication of EP0255201A2 publication Critical patent/EP0255201A2/de
Publication of EP0255201A3 publication Critical patent/EP0255201A3/de
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/029—Bipolar electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates generally to electro­chemical cells and, more particularly, this invention relates to electrodes and methods of formation thereof.
  • Electrochemical cells utilizing bipolar electrode designs having reactive metal electrodes supported on a substrate current collector are well known. See, for example, Momyer et al, U.S. Patent No. 4,269,907 (May 26, 1981), the disclosure of which is hereby incorporated by reference, wherein cells including an aqueous electrolyte, an anode of an alkali metal, such as lithium, for example, a cathode spaced from the anode, and an intercell electrical connector are disclosed.
  • the cathode may comprise an electrochemically active material, such as silver oxide
  • the electrolyte may comprise an aqueous alkaline solution.
  • Momyer et al also discloses an electrochemical cell stack comprising a plurality of bipolar electrodes connected in series.
  • bipolar electrodes wherein a cathode and an anode are disposed on opposite sides of an electrically conducting metallic substrate typically involves the oxidation/reduction of a precursor electrode material.
  • the preparation of a bipolar electrode having a silver oxide cathode typically involves oxidation of elemental silver.
  • the elemental silver is sintered and then hot forged onto a substrate current collector.
  • Nickel foil plated with silver, so as to facilitate adherence of elemental silver thereto, is commonly used as the substrate current collector.
  • the hot forgings are assembled into a stack in which the elemental silver electrodes and counterelectrodes comprising a second kind of nickel foil are alternated, with the elemental silver electrodes in the charging stack electrically connected in parallel for attachment to the positive post of a DC power supply. Further, all the nickel foil counterelectrodes are electrically connected in parallel for attachment to the negative post of the aforementioned DC power supply.
  • the stack is then placed into an electrolyte solution, permitting electrical contact between the electrodes.
  • the conventional electrode formation technique of parallel oxidation is frequently accompanied by a bending of the electrodes.
  • the silver oxide electrodes resulting from the use of the above-identified method of oxidation are frequently of a bent, irregular shape.
  • the bending of the electrode is believed to be largely a result of the stoichiometric and molar volume changes which occur upon oxidation during electrode formation and is commonly referred to as "potato chipping".
  • a system useful in the formation of electrodes for use in electrochemical cells comprises a power supply and a pair of conductive metallic terminal electrodes spaced apart from one another with at least one precursor electrode disposed therebetween.
  • the terminal and the precursor electrodes are disposed in an aqueous electrolyte.
  • the terminals are in electrical contact with the power supply effecting electric current flow in the electrolyte away from the first of the terminals and toward the second of the terminals.
  • the precursor electrode comprises a material to be reduced or oxidized and is orientated relative to the terminals so as to permit the reduction/oxidation of the material.
  • the system includes restraining means for applying restraining forces to the precursor electrode to substantially maintain the dimensions of the precursor electrode during the reduction/oxidation.
  • Separator means are disposed between the precursor electrode and the terminals and are generally effective in permitting the precursor electrode and the terminal electrodes to interface with the electrolyte while permitting a substantially uniform application of the restraining forces to the precursor electrode.
  • the invention comprehends a method of reduction/oxidation useful in the formation of electrodes for use in electrochemical cells.
  • a system and a method of reduction/oxidation useful in the formation of electrode for use in electrochemical cells is provided.
  • the invention contemplates a system having a pair of conductive metallic terminal electrodes spaced apart from one another with at least one precursor electrode disposed therebetween. During operation of the system the terminal electrodes and the precursor electrode are disposed in an aqueous electrolyte. The terminal electrodes are in electrical contact with a power supply effecting an electric current flow in the electrolyte away from the first of the terminals and toward the second of the terminals.
  • the invention may be used with precursor electrodes having various configurations provided that the precursor electrode comprise materials to be reduced/oxidized in electrical contact and orientated relative to the terminals so as to permit the reduction/­oxidation of these materials.
  • precursor bipolar electrodes of elemental silver disposed on silver clad bi-metal nickel foil is exemplary only, and the invention is understood to encompass the use of other electrode configurations and reactive metals.
  • a system, generally designated 10, useful in the formation of electrodes for use in electrochemical cells is shown.
  • the system 10 includes a pair of conductive metallic terminal or end electrodes 12 and 14 spaced apart from one another and disposed in an aqueous electrolyte 16.
  • the terminals 12 and 14 are made of nickel foil and the electrolyte may be any alkaline electrolyte such as NaOH, KOH or LiOH with KOH being preferred and KOH of a concentration of 30-45 wt% being especially preferred.
  • Fig. 1 shows three such precursor electrodes 17, individually identified as 18, 19 and 20.
  • Each of the precursor electrodes 17 comprise porous elemental silver 21 bonded to the silver side 22 of a bi-metal silver clad nickel foil 23.
  • Surrounding each of the terminal electrodes 12 and 14 and the precursor electrodes 18, 19 and 20 is a wrap of a wicking type separator 26.
  • the stack-up of the silver 21 and the nickel foil 23 are compressed together to enhance electrolyte wicking.
  • Such compressing/restraining forces may be exerted by the restraining plate walls 40 of system 10.
  • the walls 40 may be joined together by bolts and nuts (not shown) so as to permit a range of restraining forces to be produced thereby.
  • restraining forces serve to substantially maintain the dimensions of the precursor electrodes 17 during the reduction/oxidation and the consequent volumetric changes in the material 21 being reduced/oxidized.
  • the separator 26 permits the electrolyte 16 to come in contact and interface with the material 21 of each of the precursor electrodes 17 while permitting the restraining forces produced by the action of the restraining plate walls 40 to be substantially uniformly applied to the precursor electrodes 17.
  • Vexar a trademark of E.I. duPont de Nemours & Co.
  • polypropylene plastic screen material has been used effectively as the separator material 26.
  • the solid plastic parts of the screen separator 26 transmit the mechanical force being applied thereto while the openings in the screen separator 26 permit the electrolyte 16 to come in contact with the material 21 of the precursor electrodes 17.
  • a power supply 30 is electrically connected to the terminal electrodes 12 and 14, e.g., negative power supply terminal 32 is connected to terminal electrode 12 while positive power supply terminal 34 is connected to terminal electrode 14.
  • the current passing through system 10 is read by an ammeter 36 while the voltage is read by voltmeter 41 which spans and connects terminal electrodes 12 and 14.
  • the hydroxide ion so produced flows towards and to the elemental silver 21 of precursor electrode 18. Thereafter, the elemental silver 21 of the precursor electrode 18 undergoes oxidation: 2OH ⁇ + Ag ⁇ AgO + H2O + 2e ⁇ (2)
  • the terminal electrode 14 evolves oxygen.
  • the potential across the terminals 12 and 14, where hydrogen and oxygen, respectively, are evolved, is very dependent upon the current density but is in the neighborhood of 1.5V, with a silver precursor electrode being oxidized first to the univalent level followed by further oxidization to the divalent state.
  • each precursor electrode will contribute about 1.4 V until the second voltage plateau, i.e., that associated with the divalent state, is reached, whereupon the voltage increases to 1.8 V/precursor electrode.
  • the principles identified herein are capable of extension to the formation of electrodes other than the previously described bipolar precursor, including monopolar electrodes (See Fig. 2).
  • monopolar electrodes See Fig. 2.
  • two red oxidizable electrodes such as nickel oxide 21a and cadmium 23a, they may be placed together in direct contact and used to substitute for the previously described precursor bipolar silver electrode.
  • nickelous oxide (NiO) is oxidized to nickelic oxide (Ni2O3) while cadmium hydroxide is reduced to metallic cadmium.
  • the invention may also be extended to electroplating as well as any battery system in which at least one active material is a solid.
  • a metal plate may be placed over the backside of the electrode.
  • Such configuration emulates the above described precursor electrode configuration.
  • hydrogen gas evolves from the water molecules coming in contact with the metal plate while the precursor monopolar electrode is oxidized.
  • This technique can be exemplified as follows for both nickel oxide and cadmium electrodes but the principles are equally applicable to any active material suitable for secondary batteries.
  • the nickel oxide 21b When a nickel oxide electrode is to be oxidized (See Fig. 3), the nickel oxide 21b is placed into a system 10 so that it faces the terminal electrode 12 connected to the negative terminal 32 of the power supply 30.
  • the material to be oxidized 21b is mechanically separated from the negative electrode by a spacer or a separator 26 but is in electrochemical contact with the negative electrode 12 through the ionically conductive electrolyte 16.
  • the backside of the nickel oxide electrode 21b is fully covered with a coupon of metal 23b, such as nickel, which does not react with the electrolyte and on whose surface equation 1, identified above, may occur.
  • the backplate 23b is thus induced to serve as a negative electrode for the very next cell. This arrangement can then be repeated as many times as desired.
  • the nickel or other metal backplate 23b is held in electrical contact with the nickel oxide electrode 21b. Such contact may be effected by a mechanical jig or other suitable means (not shown).
  • a cadmium electrode is to be reduced (See Fig. 4), for example to later serve as an anode in a rechargeable cell, then the cadmium electrode 23c is orientated so as to face the positive electrode 14 of the system 10.
  • a foil of metal 21c, at whose survace oxygen is evolved from water, is placed in contact with the backside of the cadmium electrode.
  • a jig or fixture arrangement as previously described may be used to maintain the contact between the metal foil and the cadmium electrode.
  • a negative 21d and a positive electrode 23d can be simultaneously oxidized/reduced by placing one against the other (See Fig. 5).
  • a metal foil substrate 42 between the active materials it has been found preferable to use a metal foil substrate 42 between the active materials.
  • negative electrodes 23d generally have a greater capacity built into them than do positive electrodes 21d.
  • the oxidation/reduction process causes NI+2 to become NI +3.86 and Cd(OH)2 to become Cd ⁇ .
  • the nickel oxidation process changes to one of oxygen evolution, while the reduction of the Cd(OH)2 to Cd ⁇ continues.
  • the foil substrate 42 serves to intercede and prevent the oxygen evolving at the nickel electrode 21d from reaching the Cd ⁇ . As a consequence, oxygen is generated on the positive electrode side of the foil substrate with Cd ⁇ being generated from Cd(OH)2. In this way, both electrodes 21d and 23d may be brought to a state of maximum oxidation/reduction without significantly interfering with each other.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
EP87303942A 1986-07-28 1987-05-01 Formieren von Elektroden Withdrawn EP0255201A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/889,964 US4704194A (en) 1986-07-28 1986-07-28 Electrode formation
US889964 1992-05-29

Publications (2)

Publication Number Publication Date
EP0255201A2 true EP0255201A2 (de) 1988-02-03
EP0255201A3 EP0255201A3 (de) 1990-06-13

Family

ID=25396050

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87303942A Withdrawn EP0255201A3 (de) 1986-07-28 1987-05-01 Formieren von Elektroden

Country Status (3)

Country Link
US (1) US4704194A (de)
EP (1) EP0255201A3 (de)
CA (1) CA1293471C (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7794877B2 (en) 2005-05-03 2010-09-14 Randy Ogg Bi-polar rechargeable electrochemical battery
US8632901B2 (en) 2007-10-26 2014-01-21 G4 Synergetics, Inc. Dish shaped and pressure equalizing electrodes for electrochemical batteries
US8859132B2 (en) 2009-01-27 2014-10-14 G4 Synergetics, Inc. Variable volume containment for energy storage devices

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4681663A (en) * 1986-12-12 1987-07-21 Gould Inc. Bipolar electrode formation
US5198377A (en) * 1987-07-31 1993-03-30 Kinya Kato Method of manufacturing an active matrix cell
US4792505A (en) * 1987-12-14 1988-12-20 Westinghouse Electric Corp. Electrodes made from mixed silver-silver oxides

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE115367C (de) *
US3087033A (en) * 1959-05-04 1963-04-23 Dales George Franklin Snap thermostat
FR1377878A (fr) * 1962-12-21 1964-11-06 Procédé de fabrication d'électrodes bipolaires pour piles et accumulateurs
US3501350A (en) * 1967-04-12 1970-03-17 Carl Horowitz Method of making a silver electrode
US3671321A (en) * 1969-12-23 1972-06-20 Gulton Ind Inc Process for production and treatment of battery plates
US3784410A (en) * 1970-12-21 1974-01-08 Esb Inc Battery with duplex electrode construction using continuous metal carrier strip having at least one nonreactive metal side
US4037031A (en) * 1975-06-03 1977-07-19 Imperial Metal Industries (Kynoch) Limited Bipolar lead acid battery having titanium and zirconium electrode supports
US4269907A (en) * 1980-05-05 1981-05-26 Lockheed Missiles & Space Company, Inc. Electrochemical cell
US4637970A (en) * 1984-12-21 1987-01-20 Allied Corporation Lead-titanium, bipolar electrode in a lead-acid battery

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3671320A (en) * 1969-12-23 1972-06-20 Gulton Ind Inc Battery plate treatment process
US4172184A (en) * 1978-09-05 1979-10-23 Polaroid Corporation Laminar batteries
US4461677A (en) * 1983-07-05 1984-07-24 The United States Of America As Represented By The Secretary Of The Navy Process for charging silver electrodes to monoxide level

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE115367C (de) *
US3087033A (en) * 1959-05-04 1963-04-23 Dales George Franklin Snap thermostat
FR1377878A (fr) * 1962-12-21 1964-11-06 Procédé de fabrication d'électrodes bipolaires pour piles et accumulateurs
US3501350A (en) * 1967-04-12 1970-03-17 Carl Horowitz Method of making a silver electrode
US3671321A (en) * 1969-12-23 1972-06-20 Gulton Ind Inc Process for production and treatment of battery plates
US3784410A (en) * 1970-12-21 1974-01-08 Esb Inc Battery with duplex electrode construction using continuous metal carrier strip having at least one nonreactive metal side
US4037031A (en) * 1975-06-03 1977-07-19 Imperial Metal Industries (Kynoch) Limited Bipolar lead acid battery having titanium and zirconium electrode supports
US4269907A (en) * 1980-05-05 1981-05-26 Lockheed Missiles & Space Company, Inc. Electrochemical cell
US4637970A (en) * 1984-12-21 1987-01-20 Allied Corporation Lead-titanium, bipolar electrode in a lead-acid battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7794877B2 (en) 2005-05-03 2010-09-14 Randy Ogg Bi-polar rechargeable electrochemical battery
US8632901B2 (en) 2007-10-26 2014-01-21 G4 Synergetics, Inc. Dish shaped and pressure equalizing electrodes for electrochemical batteries
US8859132B2 (en) 2009-01-27 2014-10-14 G4 Synergetics, Inc. Variable volume containment for energy storage devices

Also Published As

Publication number Publication date
EP0255201A3 (de) 1990-06-13
US4704194A (en) 1987-11-03
CA1293471C (en) 1991-12-24

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